TW449820B - Plasma-etching electrode plate - Google Patents

Abstract

A plasma-etching electrode plate of glassy carbon which is characterized by a thickness greater than 4.5 mm and a thermal conductivity greater than 5 W/m.K at 300K. Owing to these characteristic properties, it has a uniform surface temperature distribution and permits etching on large semiconductor wafers (in excess of 8 inches in diameter) at a uniform etch rate. In addition, it is capable of stable etching for a long time and has a greatly improved durability. The glassy carbon should preferably be one which has a bulk specific gravity higher than 1.53 g/cc. The glassy carbon is obtained from one or more of thermosetting resin having a carbon yield higher than 20%.

Description

Printed by the Consumer Cooperatives of the Central Sample Bureau of the Ministry of Economic Affairs 449820 A7 _____________ B7 _ V. Description of the Invention (1) — This invention relates to the use of plasma money engraving to form wafers or crystals in the manufacturing process of semiconductor devices Improvement of electrode plate for plasma etching when thin film such as silicon oxide film on round surface. Specifically, it is an improvement of a plasma etching electrode plate manufactured using carbon as a raw material. More specifically, it is related to an electrode plate for plasma etching composed of a glass plate-like carbon plate having a uniform etching rate in processing a large wafer of 8 inches or more. That is, the present invention relates to an electrode plate for plasma-etching a silicon oxide film on a wafer surface in a manufacturing step of a semiconductor integrated circuit, and more particularly, it relates to an electrode type plasma-etching device suitable for spraying a parallel plate electrode type. Electrode plate for plasma etching made of glassy carbon plate.

Plasma etching processing system, using the single revealed by Lee Chen (USP 4534816) Single Wafer Plsama Etch Reactor "(Aug. 1.3, 1985), Mark M. (USP 4780169)" Non Uniform Gas Inlet for Dry Etching " Apparatus, 5 (Oct. 25, 1988) 'USP 423936, USP 5445709 and the like to perform this. The aforementioned etching device is provided with a lower electrode for placing a wafer substrate lower portion in a lower part of the cabin, and a pair of upper electrodes having a plurality of through holes for gas evacuation is provided on the opposite side of the upper and lower electrodes in the grab chamber as upper electrodes. Parallel planar electrodes. Reactive gases such as halogen gas and chlorochlorocarbon gas are introduced from the upper electrode side, and high-frequency power is applied between the electrodes to discharge them. The generated gas plasma is used to etch the substrate. The photoresist patterned portion is used to form a fine circuit pattern on a semiconductor wafer with high accuracy. The upper electrode used in the aforementioned plasma etching process is Lee Chen 4 This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) ('Please read the precautions on the back before filling this page) · y ---- i / f installation -----.- order -------- line --- 4 9 8 20 Α7 Β7 5 'invention description (2) Patented figure 2 or Mark.M patent As shown in FIG. 3A, a disc-shaped one is used. The shape, number, and position of the holes on the disc will vary depending on the device used, etching conditions, etc., and although not the same shape electrode plate can be used in all devices in common, but For the electric board used in each device, its shape must be strictly defined first. Furthermore, in addition to the shape of the electrode plate, it must have excellent electrical conductivity, high purity without contaminating the wafer, and chemical stability of the electrode plate not easily being etched. Therefore, the electrode material is made of aluminum, stainless steel, carbon (graphite), etc. Now, glass-like carbon materials that meet the requirements of the above materials are used to form the electrode plate. Slope-like carbon materials are generally hard carbon materials with non-porous structure obtained from carbonized thermosetting resins. Although they have high strength, low chemical reactivity, gas impermeability, self-lubricity, fastness, and impurities Less characteristics, especially compared with other materials, because its fine particles are not easy to detach from the organization, so it is not easy to cause wafer fouling in the plasma etching process. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the back note ^^ before filling out this page) However, with the increase of semiconductor accumulation, for electrode materials for plasma etching, in addition to the shape In addition, physical and chemical properties are also required. Therefore, it is necessary to reduce the amount of particles and consumption on the wafer surface. Therefore, many attempts have been made so far to improve the material of the glass electrode for plasma etching. For example, to improve properties such as purity, porosity, pore size, and crystal structure, Japanese Patent Application Laid-Open No. 3-33007 suggests using a porosity of 0'0002 to 0.0020%, and preventing the use of X-ray diffraction to detect microcrystals, and Miscellaneous papers are printed from _Cai Zhuan (CNS) Α Outline (格 χ297 & 4) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 449320 A7 _____B7 * 5. Description of the invention (3) Glassy carbon materials with a mass content of 5PPm or less A carbon element for a plasma device constructed; EP421686B1 discloses an electrode plate for plasma etching using high-purity glassy carbon having a maximum pore size of 1 μm or less, an average pore size of 0.7 μm or less, and a porosity of 1% or less; Japan Japanese Patent Application Laid-Open No. 3-285〇86 discloses that plate-like bodies with a thickness of at least two faces, surfaces, and internal structures made of high-purity glassy carbon do not have substantial grain boundaries, and have a maximum pore size of 1 μm or less for plasma etching. Electrode plate; Japanese Patent Application Laid-Open No. 5_32〇955 discloses that the purity characteristics are 5 ρρηι or less, 2 ppm or less of metal impurities, 30 PPm or less of total sulfur, and the crystal characteristics are crystalline. Plasma etching electrode plate made of glassy carbon with interplanar space (〇〇2) or less than 375 nm, microcrystalline (002) size of 13 nm or more, material characteristics of specific gravity j 50 or more, and meandering strength 1100 kg / cm2 or more Japanese Unexamined Patent Publication No. 6-128761 discloses an electrode for plasma etching composed of glassy carbon having crystals having a lattice constant CG of 6.990A or less. In addition, Japanese Unexamined Patent Publication No. 6 -12 8 7 6 2 discloses surface electrode as an object, and discloses the electrode plate for plasma etching composed of «consumed surface smoothness of inversely less than one glassy carbon; Japanese Patent Application Laid-Open No. 347276 discloses an electrode plate for plasma etching composed of glass-breaking carbon produced by using a resin and polycarbodiimide as raw materials for a technique for specifying a raw material system of glassy carbon. ^, Japanese Unexamined Patent Publication No. 4-362062 and Japanese Unexamined Patent Publication No. 100365 disclose a method for producing glassy carbon having a considerable thickness. One of the important technical elements in electrical engraving is the engraving rate (speed). In order to improve the processing accuracy, the uniform etching rate must be ensured 6 (Please read the precautions on the back before filling this page)

Printed by the Employees' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 498498 Α7 ---------- B7 V. Description of Invention (4). The uniformity of the remaining rate is obviously governed by the temperature of the reaction part, especially the temperature distribution on the surface of the electrode plate. Therefore, when the surface temperature changes, a uniform and stable etching rate cannot be obtained. Therefore, for thin electrode plates, in order to maintain uniform temperature of the electrode plates that generate heat by irradiation with electric paddles, a metal cooling plate is usually adhered to the inside of the electrode plates to form a laminated state. At this time, if the electrode plate is thin, the electrode plate itself is prone to bending. When tube bending occurs, it will lead to poor contact with the electrode cooling plate, which will prevent heat generation. Therefore, it is necessary to make the plate bend as much as possible. The method of making the ground smaller 0 However, thicker electrode plates are better than thinner electrode plates. The reason is that thicker plates can withstand consumption and can be used stably for a long time without generating electrode plates. The need to stop the operation of the device. Recently, with the high integration of semiconductor devices, circuit patterns have become increasingly finer. And since the wafer size has been formed to be more than 8 inches, and it is about to exceed 12 inches, it is important to accurately etch and process large wafers. The technical problem is the uniformization of the etching rate. However, no attempt has been made so far to improve the uniformity of the etching rate from the material surface of glassy carbon constituting the electrode. The main reason for controlling the etching rate is the temperature of the reaction system. Especially in electrode plates with a thick thickness, an important condition for achieving uniformity of the remaining rate is to maintain the temperature distribution on the surface of the electrode plate uniformly. The aforementioned Japanese Unexamined Patent Publication No. 4-362062 and Japanese Unexamined Patent Publication No. 6-100365 disclose glass-like carbon having a thick plate thickness, but these materials do not exhibit sufficient charging characteristics when used as a plasma-etched electrode plate. 7 Yuzhang scale Guzhong® 1 home turn (CNS) Α4 size (21G X 297 mm) (Please read the note on the back Jt climbing item before filling out this page)

449820 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the Invention (5) The inventor is to solve the problems in the conventional glass-breaking electrode plate for plasma etching, based on the above-mentioned knowledge. The relationship between the properties of the glassy carbon electrode plate and the etching rate was reviewed in various aspects. As a result, it was found that when the thermal conductivity of the glassy carbon material constituting the electrode plate was above a certain 値 and the thickness of the electrode plate was above a predetermined 値In this case, the temperature distribution on the surface of the electrode plate can be equalized, so that processing can be performed at an excellent etching rate. The object of the present invention is to provide an electrode plate for plasma etching, which can uniformize the etching rate by equalizing the temperature distribution on the electrode surface, and can perform etching processing stably for a long time even for a large wafer exceeding 8 inches. A feature of the electrode plate for plasma etching of the present invention for solving the above-mentioned problems is that it is composed of a glassy carbon plate having a thermal conductivity of 5 ° / 111 ° C at a temperature of 300 ° C and a thickness of 4.5 or more. Because the present invention is to uniformize and stabilize the temperature of the electrode plate for plasma etching with a thickness of 45 or more, to equalize the temperature distribution of the plasma generation surface of the electrode plate, thereby achieving uniformity of the semiconductor wafer. For the purpose of etching speed, therefore, the electrode plate has the following requirements: it is a flat disk-shaped electrode with a large number of through-holes composed of glassy carbon villages, and its specific gravity after grinding is 1.53g / cc or more And has a thermal conductivity of 5 W / m · κ or more. [Brief description of the drawing] Fig. 1 shows the relationship between the thermal conductivity and the uniformity of the etching rate (E / R) when 2000 hours have passed. Figure 2 shows the thermal conductivity and the paper size of the electrode sheet when 200 hours have elapsed. _ 家 转 (CNS) (Please read the precautions on the back before filling out this page Printed by the staff of the Municipal Bureau of Cooperatives 449820 A7 ___ B7 5. Description of the invention (6) Relationship between surface consumption. Figure 3 shows the relationship between the overall density and the surface consumption of the electrode plate after 200 hours. [Preferred implementation Morphology]. The electrode plate for plasma etching of the present invention is preferably based on the premise that it is composed of a glassy carbon plate with a uniform structure obtained by sintering a thermosetting resin with a carbonization rate of 20% or more, and its purity characteristics: High-purity materials with a total ash content of 5 ρριη or less, metal impurities of 2 ppm or less, and a total plate content of 3 Oppm or less. Flat surfaces with the highest possible surface smoothness. This prevents impurities from diffusing to the wafer and particles (small foreign matter) from falling. Therefore, the carbonization rate is the residual rate of carbon, which is the weight of carbon remaining when sintered at 800 to 1000 eC in a non-oxidizing ambient gas.

V Furthermore, the important physical property conditions of the present invention are: among the electrode plates for plasma cooking, the glass-like carbon plate has a thermal conductivity at a temperature of 300K of 5W / mK or more, a thickness of 4.5 mm or more, and an overall density of i.53g / cc 玻璃 A glassy carbon system with a large thermal conductivity and a large thickness. Since the thermal conductivity of the electrode plate is small due to its good thermal conductivity and large amount of thermal valleys, the surface temperature can be equalized, so the etching rate can be maintained at a high level. Uniformity. Furthermore, the aforementioned effects can be further enhanced by increasing the overall specific gravity, and therefore the consumption resistance under plasma can also be improved. However, for glassy carbon with a thermal conductivity of less than 5 W / m K or a thickness of less than 4 · 5 faces at a temperature of 300 K, the temperature is easily caused by the temperature fluctuation of the electrode plate due to the heat generated by plasma etching and the like. It is not easy to form uniformity, and as a result, the uniformity of the etching rate is deteriorated. -· ----- --1 1-.-1. 丨-*--n ^ i 'r___I. — ^ — ^ 1 — ^^ 1 11 i--II-aJ11- i— —-ill- -(Please read the precautions on the back before filling this page) This paper size _ (CNS) Α4ϋΤ210 × 297 ^) '〇2〇 by #outside Central Standards Bureau + Industrial and Consumer Cooperatives printed A7 B7 V. Description of the invention (7) Based on Therefore, since the electrode plate for plasma etching of the thick plate-thick glassy carbon plate of the present invention has a large heat capacity, it does not reduce the adhesion with the cooling plate due to bending or the like in a thin plate electrode plate. problem. That is, the requirement of the present invention is to effectively limit the variation of the surface temperature distribution by clearly limiting the range of the thermal conductivity and the thickness, so that the uniformity of the etching rate is practically excellent. The thick and thick electrode plate system has excellent handling properties when processing large wafers, and has the effects of prolonging electrode life. A glassy carbon system having the above-mentioned properties. For example, a phenol or a derivative thereof is mixed into a phenol resin having a molecular weight of 1,000 or more and a gelation time of 5 to 60 minutes to form a viscosity of 1 to 100 poises and a resin content of 50% by weight. The resin composition is manufactured by molding and hardening the resin composition in a non-oxidizing ambient gas by sintering and carbonization. In general, thick glass-like carbon plate systems tend to have a structural difference between the external and internal carbon crystals, such as the degree of development and compactness, that is, the difference between the internal and external structures. This tendency tends to increase with the increase in thickness. Significantly, it will increase the probability of cracks and other occurrences during heat treatment. However, during the aforementioned manufacturing process, the design of the raw material system, the setting of the heating temperature of the resin composition, the final hardening temperature, the uniform heating during sintering and carbonization, the setting of the heating rate or heating conditions, and the setting of the final sintering temperature are strictly controlled. Conditions, a glassy carbon plate that satisfies the physical properties of the present invention can be manufactured. That is, in order to satisfy the characteristics of the glassy carbon as the specific electrode etching electrode pile of the present invention, a suitable manufacturing method is one that is processed in accordance with the following manufacturing steps. Paper money is subject to Chinese National Standard (CNS) A4 & (2) 〇 X 297 mm (Please read the notes on the back before filling this page)

S11-J. H ， II I * · ^,-I ..... I Order -----Buxian --------! ---- 1. 449820 Central Bureau of Standards, Ministry of Economic Affairs Printed by the buyer's consumer cooperative A7 B7 V. Description of the invention (8) ① The adjustment and molding steps of the raw resin use phenol and '" Hanan thermosetting resin as raw materials. The specific manufacturing steps are shown below. First, the refined phenol and formalin are used as raw materials to obtain a pre-condensate with a molecular weight of more than 00 and a time of victory by condensation reaction. A two-component resin composition having a carbonization yield of 65 to 75% was formed. In this case, the < > furan derivative used may be those having compatibility with furan resin, such as furfuryl alcohol, furfural, methyl p-furan carboxylate, etc., and may be used alone or in combination of two or more. The blending ratio of the blowing-system component to the phenol resin can be set to match the properties of the tree deer to adjust the properties of the two-component resin to a viscosity of 50% or more. Next, by column molding, centrifugal molding, injection molding, etc., the Shuyue E1 composition is formed into a disc shape with a thickness of 4.5 mm or more like a glassy carbon plate finally obtained, and then heat-hardened . When using polycarbodiimide-based raw materials, 2,4-toluene diisocyanate, 2,6 · toluene diisocyanate, or a mixture thereof, crude toluene diisocyanate, xylene diisocyanate, M-phenyl diisocyanate, cold-1,5-diisocyanate, 4,4'-diphenylene diisocyanate, 3,3, dimethoxy 4,4'-diphenyl diisocyanate and other aliphatic System, cycloaliphatic system, aromatic system, or these quinone compounds or copolymers thereof; these raw materials can be disclosed according to Japanese Unexamined Patent Publication No. 51-61599 and Japanese Unexamined Patent Publication No. 2-292316. Method. A polymerization catalyst is added to these organic diisocyanates and reacted, followed by heating to harden the formed body after removing the solvent. ② Hardening step 'This paper ^^^ National National Standards (CNS) Μ specifications (21〇χ-297 public flood) (Please read the precautions on the back before filling in this page). Loading. Staff of the Central Bureau of Standards, Ministry of Economic Affairs Printed by the Consumer Cooperative 449820 A7 ________________B7_ V. Description of the Invention (9) " ~ In this step, firstly based on the fact that the glassy carbon plate finally obtained when the hardened formed body has internal and external differences in structure and structure will also appear based on the end The degree of development of the crystal is poor inside and outside, so the hardening conditions must be strictly controlled. Generally, the hardening of a thermosetting resin is an exothermic reaction. As the thickness is thicker, the hardening of the surface layer will proceed first. Therefore, when the dehydration or drying is to be completed quickly and the skin is heated rapidly, the skin effect will occur and the outer layer will be the first Cure and densify. As a result, it becomes difficult to remove the water or the reaction generated gas inside the resin composition that is generated by the hardening reaction. Therefore, in order to avoid such uneven curing of the resin molded body, the temperature rise rate during heat curing must be adjusted to 10 X / hour or less, preferably 5 C / hour or less, and more preferably 2 ° C / hour or less. Next, the heating temperature is raised to the temperature at the end of the curing reaction, and the temperature is maintained at this temperature for a sufficient time so that the inside of the resin molded body can be completely cured. Although the curing temperature varies depending on the composition of the resin, the type of the curing agent, and the blending, it is usually maintained at 14 to 200. (: Within the temperature range, and in the case of the polycarbodiimide-based resin, it is preferably maintained at 2000 to 25 (rc ^^.) To maintain the curing temperature above the holding time required for complete curing. ③ The sintering and carbonizing step puts the hardened resin molded body in a heating furnace maintained under a non-oxidizing ambient gas, and performs sintering and carbonizing treatment at a temperature range of 80CTC or more to transform into a glass-like carbon plate. Due to the heat conduction of the resin hardened material The rate is low, so when the thickness is thick, the decomposition and carbonization reaction of the internal structure during the sintering and carbonization process is slower than the vicinity of the surface calendar part. Therefore, with the first carbonization near the surface layer part, the interior will be under tension. Carbonization, the result is easy to apply the Chinese National Standard (CNS) Λ4 specification (21〇 > < 297mm) at 12 paper sizes (please read the note on the back before filling this page)

449820 A7 B7 5 10 Printed by the Consumer Cooperatives of the Central Bureau of Quasi-Equipment of the Ministry of Economic Affairs of the People's Republic of China \! Difference in thermal conductivity between the surface layer and the interior. In order to alleviate this phenomenon, the heating rate of sintering carbonization is set to 2 ° C / hour or less, and the inner and outer layers are carbonized at a uniform rate by slowly increasing the temperature. Although glassy carbon has gas impermeability, in fact, there are many ultrafine gases 1 in its structure, and its crystal is non-uniformly amorphous, which is different from graphite-like crystalline carbon. When sintering and carbonizing, there will still be pores inside the structure, which will reduce the overall density. Furthermore, the presence of stomata increases the thermal insulation effect, and therefore reduces the heat capacity. When it is ready to continuously form bubbles or bubbles grow out, the result will be the same as the formation of holes in the material, that is, the strength will be reduced, and cracks will easily occur in the carbonization step, so it is difficult to obtain a thick Plate thickness products. Furthermore, when there are many bubbles, the pores are exposed when the electrode is consumed and the edges are formed on the electrode surface due to the difference in the use conditions. Therefore, selective consumption occurs, which means that the particles are likely to peel off due to the formation of particles. After the hardening is completed, the resin molded body is sandwiched between graphite plates, thereby being placed in a graphite crucible under pressure and placed in a heating furnace, while adjusting the pressure conditions of the furnace match to 800 ~ 2500 ° The sintering carbonization temperature is adjusted within the range of C to thereby produce glassy carbon plates with different thermal conductivity. In addition, in the temperature rise process of sintering carbonization, the effective method to reduce the difference between the internal and external structure is' in the temperature region where the carbonization is intensely decomposed, the temperature where the gas is intensely generated, and the temperature region where the carbonization is completed and the structure is changed. Perform temperature maintenance. Specifically, it is maintained for 5 hours at each temperature stage of 300-400 (Ke, 400-500 eC, and 500-600 ° C).

please ! Read first | Read S ί I Note 丨. Item-· Fill in I Outfit I I Order-Line 13 This paper is fully compliant with China National Standard (CNS) Α4 Specification (2ί〇 × 297 mm) 449820

Printed by the Central Bureau of Standards of the Ministry of Economic Affairs on Consumer Consumption by Du. V. Invention Description (11 above) The reason is that even if the temperature is continuously raised below 2 ° C, the internal pressure may rise sharply due to the presence of air bubbles. Causes the destruction of the entire material structure. Therefore, by adopting the aforementioned method that can suppress the growth of bubbles, a glassy carbon material with a high overall density and a large thermal conductivity can be obtained. The additional effect of reducing bubbles is that it can be effective In order to suppress the structure collapse and excessive consumption of the electrode during use, as a result, the consumption of the electrode can be uniformized and the etching rate can be increased. In addition, other methods for obtaining a thick plate and a thick product are mixing carbonaceous materials, easy carbonization < organic materials, or Add the metal elements or metallizing substances that can combine and remove the water and gas generated by the special reaction. However, when the third component is used as such, when these substances or the powders formed by these substances are changed in When the electrode is consumed and falls on the wafer, the problem of so-called particles occurs, so the particle size of these additives must be 2 μm or less. ④ High purity After the sintering and carbonization, if necessary, the glassy carbon plate is processed at a high temperature of 1400 ° C or higher by introducing gaseous gas from the element into the furnace, as necessary. ⑤ Formation of through-holes In addition, the gas flow provided in the electrode plate is generally penetrated through the small hole system, and it can be worn at the resin molding stage ② to estimate the dimensional shrinkage rate during carbonization, or it can be worn by discharge processing of the resin plate after sintering. The specific examples and comparative examples of the present invention will be specifically explained, but the paper size of this issue applies to the Chinese National Standard (CNS) μ specification (21〇χ297 public fee) (please read the precautions on the back before filling this page) 449820 A7 B7 5. The description of the invention (12) is not limited to these examples. The raw materials used can be phenolic resins, urethane resins, polyamide resins, and polycarbodicarbonates with a carbonization rate of 20% or more. Amine resin, or a thermosetting resin obtained by mixing these resins in an appropriate amount. (► > Examples 1 to 13, Comparative Examples 1 to 6 (1) Manufacturing of electrode plates for plasma etching Resin as An example of the material is described, and the hope and the formaldehyde refined through the reduced pressure steaming hall are subjected to a condensation reaction in the presence of ammonia to prepare a phenol resin prepolymer having a molecular weight and a gelation time as shown in Table j, respectively. Add 30 parts by weight of furfuryl alcohol to 100 parts by weight of the resin and mix to obtain a resin composition with a viscosity of 40 poise and a resin content of 55%. The resin composition is flowed into a polyethylene bucket and placed in an air dryer. After defoaming under a reduced pressure of 1 OTorr, it was transferred to an electric furnace and heated to 200 ° C at a temperature rise rate of 4 ° C / hour. The temperature was maintained for 5 hours, and a hardening treatment was applied to form the product. Plate shaped body. (Please read the precautions on the back before filling this page).

Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economics of the 1T Line 15 This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 4 4 Qing 1δ68 Patent Specification Amendment. 7 7 Date of amendment: 89.08.11 Invention Description (13

.5- Table Example No. Gelation time (minutes) of the average molecular weight of the variable piece Furnace pressure (Torr) Sintering temperature (.0 1 132 14 800 2000 Solid 2 132 14 1500 2000 3 132 14 800 2200 4 132 14 2000 2500 5 132 14 1500 2500 Application 6 125 18 800 2000 7 125 18 800 2000 8 125 18 800 2500 Example 9 125 18 2000 2000 10 125 18 2000 2500 11 125 18 800 1700 12 125 18 2000 1500 13 125 18 2000 1500 1 125 18 2000 1500 2 132 14 2000 2500 to 3 132 14 800 1400 to 4 125 18 800 2000 Example 5 125 18 500 1700 6 125 18 800 1500 Next, a graphite sheet with a thickness of 10 mm [manufactured by Tokai Carbon Co., Ltd., G347] The two side surfaces of each plate-shaped formed body were sandwiched and placed in a graphite crucible, and the furnace was placed in an electric furnace maintained under an argon atmosphere to perform sintering and carbonization treatment. At this time, the furnace was changed by argon gas in the electric furnace. When the temperature is gradually increased at a temperature of 1 ~ 4¾, the JL is maintained at the temperature of 350 * C and 55C for 5 hours during the sintering process, and is processed at the final predetermined temperature (sintering temperature). The furnace pressure and sintering temperature are as follows This is shown in Table 1. In addition, while letting the chlorine gas flow through the inside, it is the same as the sintered carbonized paper. This paper size is applicable to the Chinese National Standard (CNS) A4 specification (21CM 297 mm) (Please read the precautions on the back first) (Fill in this page again) ------- Order --------- Line I. Consumer cooperation of Intellectual Property Bureau of the Ministry of Economic Affairs Du printed 449820 A7 ___ _B7. V. Description of Invention (14) ~~ The high-purity treatment is carried out at a temperature of the final processing temperature at ~~~ to produce glassy carbon plates with smooth surfaces of different diameters and thicknesses. The obtained glassy carbon plate is passed through the center portion by electric discharge machining 2 Electrode plates for plasma erosion swords were manufactured with uniformly spaced through-holes with a diameter of 0.5 legs. Table 2 shows the physical properties of each glassy carbon plate compared to the variable conditions during manufacture. Thermal conductivity in physical properties Measured in accordance with JIS Rl6n_199l. Among them, the standard sample of specific heat capacity is high purity ... oxide, the light receiving plate is blackened aluminum, and the standard sample of thermal diffusivity is high purity copper. The total density was measured by Archimedes (method of weighing in liquid) in accordance with JIS Z8807-1987. (Please read the precautions on the back before filling in this page.) 2. Print out a table printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. Example No. Conductivity (W / m-ΚΊ Thickness (mm) Overall Density (r / cc) Diameter imnn example 1 2 3 4 5 6 7 8 9 10 11 12 13 5.2 5.9 5.8 7.2 6.6 5.8 5.7 6.5 6.3 7.2 5.2 5.0 5.0 4.5 5.0 5.0 8.0 6.0 6.0 6.2 5.0 6.0 6.0 5.0 5.0 5.0 1.52 1.55 1.52 1.59 1.55 1.54 1.54 1.56 1.55 1.59 1.53 1.54 1.54 — \ ****** I 300 300 380 380 380 300 390 300 200 300 300 300 380 1 2 5.2 7.2 4.0 4.0 ~~ L50 ~~~~ 1.58 300 380 300 ratio 3 4.1 5.0 1.53 ratio 4 5.7 4.1 1.53 300 200 Example 5 4.9 3.5 1.50 6 4.8 4.1 1.51 300 17-Ordering the paper size Applicable to China National Standard (CNS) 8 Appearance (21〇 > < 297 mm) 449820 A7 B7 V. Description of the invention (15) (2) Performance evaluation of electrode plate Each electrode plate composed of a glass-like broken plate having physical properties in Table 2 was set in a plasma etching apparatus, and sand wafers were measured after a processing time of 100 and 200 hours. The uniformity of the remaining time is shown in Table 3. Table 3 Example No. Treatment Period E / R uniformity (%) 200 hours during 100 hours processing E / R uniformity (%) Consumption (mm) E / R uniformity (%) Consumption (min ') 1 3.1 3.2 0.65 3.4 , 1.00 Real 2 2.6 2.5 0.39 2.8 0.80 3 3.0 3.2 0.79 3.3 1.10 4 2.4 2.5 0.17 2.7 0.37 Application 5 2.5 2.7 0.36 2.8 0.75 6 3 · 1 3.3 0.36 3.5 0 77 7 2.8 2.9 0.38 3.3 0 80 Case 8 2.7 2.8 0.35 3.1 0 74 9 10 2.6 2.9 0.31 3.2 0 64 2.2 2.2 0.30 2.5 0 55 11 3.0 3.2 0.43 3.3 0 88 12 13 3.3 3.4 3.5 3.5 0.46 0.55 3.6 3.8 0.85 〇95 Comparative Example 1 2 3 4 5 6 4.1 3.7 5.5 4.2 4.6 4.4 5.3 4.6 7.2 4.4 5.1 4.7 ~ 〇T79 0.97 0.51 0.61 0.64 0.75 6.5 5.2 8.6 4.7 5.2 4.9 1.60 1.98 1.30 1.25 1.30 1.58 Money engraving processing system, please (please read the precautions on the back before filling this page)-binding-binding ΙΪ Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs · Reaction gas: CF4 Carrier gas: Argon Gas pressure in the reaction chamber: 1 Torr Power frequency: 13.5MHz For the oxide film of S-inch silicon wafers History 18 This paper size applies to Chinese National Standards (CNS ) A4 specification (2 丨 〇 · 〆297mm) ---- 449820 A7 B7 Printed by the Central Laboratories of the Ministry of Economic Affairs, Shelley Consumers' Cooperative, and description of the invention (16) In addition, the electrode consumption is the treated electrode The thickness of the plate is reduced; the uniformity of the remaining rate (E / R uniformity) is obtained based on the etching rate including 9 points of the wafer center according to the following formula. Γ, (J, / n / NI maximum 値 -min 値, ΛΛ 5 / i? Homogeneity (/.) = Soil maximum profit & small 値 χίοο. Based on the results of Tables 2 and 3, the etching will be performed after 200 hours The relationship between the uniformity of the velocity and the thermal conductivity, the consumption of the electrode plate surface, and the thermal conductivity are shown in Figures 1 and 2. The glassy carbon plate with a thermal conductivity of 300 W at a temperature of 5 W / mK or more and a thickness of 4.5 mm or more is shown in Figures 1 and 2. The electrode plate system for plasma etching according to the embodiment is compared with the comparative example which does not meet any of the requirements of the present invention. It can be seen that the fork electrode has excellent uniformity of the etching rate even after a long period of time. The consumption of the surface of the plate is also small. Moreover, as shown in FIG. 3, when the embodiment has the characteristic that the overall density of the glassy carbon plate is 1.53 g / cm3, it can be found that in addition to the uniformity of the etching rate It has excellent performance of reducing consumption rate. As mentioned above, according to the present invention, by selecting a glassy carbon plate having a thermal conductivity at room temperature or higher and a predetermined thickness or more, it can provide uniformity. Processing of large semiconductors at etch rates Electrode plate for high-performance plasma etching of wafers. Therefore, in addition to long-term use, it can ensure stable and engraved processing. At the same time, it can greatly improve the durable life of the electrode plate, so it has a considerable industry Contributions I .:. --- do clothing-(Please read the notes on the back before filling in this page),-=-Line 19 Each paper * size applies to China National Standard ([阳] 8 4 specifications (2 丨〇;? ≪; 297 citizenship :)

Claims (1)

No. 86101568 ^ Specialty Fan Garden _ ^^ lAfh / 丨 Sun 丨 Even ii λ 11 j η-A 1 \ B8 Corrected date ^ ⑽ C8 D8 UJ-- /) S 4 4 9 b ^ u] 1 yu, VI. Apply for patent Yulei · 一 ΤΐΓ U 1. An electrode plate for plasma etching, which is maintained at 300 ~ 400 ° C for more than five hours and 400 ~ 500. (: Carbonized firing step that is held for more than five hours and 500 to 600 eC for more than five hours and has a thermal conductivity of 5 to 7.2 W / m.K 'at a temperature of 300K and a thickness of 4.5 mm or more for a glassy carbon plate Composition. 2. The electrode plate for plasma etching according to item 1 of the patent application park, wherein the overall density of the glassy carbon plate is 1.53 g / cc or more. The electrode plate for plasma etching described above, wherein the glassy carbon plate is manufactured using a resin composition composed of one or two or more thermosetting resins having a carbonization rate of 20% or more as a raw material. Read the precautions below before filling in this K) The paper printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs applies to Chinese National Standard (CNS) A4 (210 X 297 mm)